Fluorinated ether compound, fluorinated ether composition, coating liquid, article and its production method

ABSTRACT

To provide a fluorinated ether compound capable of forming a surface layer excellent in fingerprint stain removability and abrasion resistance as before and more excellent in light resistance than ever. 
     A fluorinated ether compound represented by A 1 —O—(R f1 O) m —A 2 , wherein A 1  is a perfluoroalkyl group or the like, A 2  is —Q 1 [—C(R 11 ) b (R 12 ) 3−b ] a  or the like, R f1  is a fluoroalkylene group, m is from 2 to 500, Q 1  is a a+1 valent organic group, R 11  is —Q 2 —Si(R 21 ) c (R 22 ) d (R 23 ) e , R 12  is a hydrogen atom, a halogen atom or the like, a is an integer of from 1 to 3, b is 2 or 3, Q 2  is a single bond or a bivalent organic group, R 21  is —Q 3 —Si(R 31 ) 3−g (R 32 ) g , R 22  is an alkyl group, R 23  is a hydrolyzable group or a hydroxy group, c, d and e are from 0 to 3, c+d+e is 3, c in at last one R 11  among a plurality of R 11  is 2 or 3, Q 3  is a bivalent organic group, R 31  is an alkyl group, R 32  is a hydrolyzable group or a hydroxy group, and g is from 1 to 3.

TECHNICAL FIELD

The present invention relates to a fluorinated ether compound, afluorinated ether composition, a coating liquid, an article and itsproduction method.

BACKGROUND ART

A fluorinated ether compound having a poly(oxyperfluoroalkylene) chainis capable of forming on a surface of a substrate a surface layer havinghigh lubricity, water/oil repellency, etc. and thus is suitably used fora surface treatment agent. A surface treatment agent containing thefluorinated ether compound is used in an application where it is desiredto maintain, for a long period of time, a performance (abrasionresistance) whereby water/oil repellency is less likely to be loweredeven if the surface layer is rubbed repeatedly with fingers, and aperformance (fingerprint stain removability) whereby a fingerprintadhering to the surface layer can be readily removed by wiping, forexample, as a surface treatment agent for a member constituting a planeof a touch panel to be touched with fingers, a spectacle lens, a displayof a wearable terminal, etc.

As a fluorinated ether compound capable of forming on a surface of asubstrate a surface layer excellent in abrasion resistance andfingerprint stain removability, the following has been proposed.

A fluorinated ether compound which has a poly(oxyperfluoroalkylene)chain and three hydrolyzable silyl glurps introduced to one terminal ofthe chain via a branch by a carbon atom (Patent Document 1).

A fluorinated ether compound which has a poly(oxyperfluoroalkylene)chain and two hydrolyzable silyl groups introduced to one terminal ofthe chain via a branch by a nitrogen atom (Patent Document 2).

PRIOR ART DOCUMENTS Patent Document

Patent Document 1: WO2017/038830

Patent Document 2: WO2017/038832

DISCLOSURE OF INVENTION Technical Problem

The fluorinated ether compounds in Patent Documents 1 and 2 areexcellent not only in fingerprint stain removability and abrasionresistance but also in light resistance. In recent years, a surfacelayer of e.g. a member constituting a plane of a touch panel to betouched with fingers is required to have further improved lightresistance. Accordingly, a fluorinated ether compound capable of forminga surface layer more excellent in light resistance while maintainingfingerprint stain removability and abrasion resistance, may sometimes berequired.

An object of the present invention is to provide a fluorinated ethercompound capable of forming a surface layer excellent in fingerprintstain removability and abrasion resistance as before and more excellentin light resistance than ever; a fluorinated ether composition and acoating liquid containing the fluorinated ether compound; an articlehaving a surface layer excellent in fingerprint stain removability andabrasion resistance as before and more excellent in light resistancethan ever; and a method for producing it.

Another object of the present invention is to provide a fluorinatedether compound useful as an intermediate of a fluorinated ether compoundsuitably used for a surface treatment agent.

Solution to Problem

The present invention provides a fluorinated ether compound, afluorinated ether composition, a coating liquid, an article, a methodfor producing an article, and another embodiment of a fluorinated ethercompound, having the following constitutions [1] to [13].

-   [1] A fluorinated ether compound, which is a compound represented by    the following formula (1):    A¹—O—(R^(f1)O)_(m)—A²   (1)-    wherein A¹ is a C₁₋₂₀ perfluoroalkyl group, a group represented by    the following formula (g1-1), a group represented by the following    formula (g1-2) or a group represented by the following formula    (g1-3),    -   A² is a group represented by the following formula (g1-1), a        group represented by the following formula (g1-2) or a group        represented by the following formula (g1-3),    -   R^(f1) is a fluoroalkylene group,    -   m is an integer of from 2 to 500, and    -   (R^(f1)O)_(m) may consist of two or more types of R^(f1)O        differing in the number of carbon atoms:        —Q¹[—C(R¹¹)_(b)(R¹²)_(3−b)]_(a)   (g1-1)        —Q¹[—N(R¹¹)₂]_(a)   (g1-2)        —Q¹[—Z(R¹¹)_(n)]_(a)   (g1-3)-    wherein Q¹ is a a+1 valent organic group (provided that the    terminal bonded to the terminal oxygen atom of O(R^(f1)O)_(m) is CF₂    or CHF),    -   Z is a group having a n+1 valent cyclic structure having a        carbon atom or a nitrogen atom to which Q¹ is directly bonded        and a carbon atom or a nitrogen atom to which R¹¹ is directly        bonded,    -   R¹¹ is a group represented by the following formula (g2),    -   R¹² is a hydrogen atom, a halogen atom, a hydroxy group or a        monovalent organic group,    -   a is an integer of from 1 to 3,    -   b is 2 or 3,    -   n is an integer of at least 2,    -   when a is at least 2, the a [—C(R¹¹)_(b)(R¹²)_(3−b)] may be the        same or different, the a [—N(R¹¹)₂] may be the same or        different, and the a [—Z(R¹¹)_(n)] may be the same or different,        and    -   a plurality of R¹¹ may be the same or different;        —Q²—Si(R²¹)_(c)(R²²)_(d)(R²³)_(e)   (g2)-    wherein Q² is a single bond or a bivalent organic group,    -   R²¹ is a group represented by the following formula (g3),    -   R²² is an alkyl group,    -   R²³ is a hydrolyzable group or a hydroxy group,    -   c, d and e are each independently an integer of from 0 to 3,    -   c+d+e is 3,    -   in at least one R¹¹ among a plurality of R¹¹ in each of A¹ and        A², c is 2 or 3,    -   when c is at least 2, the c R²¹ may be the same or different,    -   when d is at least 2, the d R²² may be the same or different,    -   when e is at least 2, the e R²³ may be the same or different;        —Q³—Si(R³¹)_(3−g)(R³²)_(g)   (g3)    -   wherein Q³ is a bivalent organic group,    -   R³¹ is an alkyl group,    -   R³² is a hydrolyzable group or a hydroxy group,    -   g is an integer of from 1 to 3,    -   when g is 1, the two R³¹ may be the same or different, and    -   when g is at least 2, the g R³² may be the same or different.-   [2] The fluorinated ether compound according to [1], wherein a is 1.-   [3] The fluorinated ether compound according to [1] or [2], wherein    Q² is a single bond or a C₁₋₆ alkylene group.-   [4] The fluorinated ether compound according to any one of [1] to    [3], wherein Q³ is a C₂₋₆ alkylene group.-   [5] The fluorinated ether compound according to any one of [1] to    [4], wherein A¹ is a C₁₋₂₀ perfluoroalkyl group.-   [6] A fluorinated ether composition comprising at least one type of    the fluorinated ether compound as defined in any one of [1] to [5],    and other fluorinated ether compound.-   [7] A coating liquid comprising the fluorinated ether compound as    defined in any one of [1] to [5] or the fluorinated ether    composition as defined in [6], and a liquid medium.-   [8] An article comprising a substrate and a surface layer formed of    the fluorinated ether compound as defined in any one of [1] to [5]    or the fluorinated ether composition as defined in [6] on a surface    of the substrate.-   [9] The article according to [8], which has the surface layer on a    surface of a member constituting a plane of a touch panel to be    touched with fingers.-   [10] A method for producing an article, which comprises treating a    surface of a substrate by dry coating method using the fluorinated    ether compound as defined in any one of [1] to [5] or the    fluorinated ether composition as defined in [6] to form a surface    layer formed of the fluorinated ether compound or the fluorinated    ether composition on the surface of the substrate.-   [11] A method for producing an article, which comprises applying the    coating liquid as defined in [7] to a surface of a substrate by wet    coating method, followed by drying to form a surface layer formed of    the fluorinated ether compound or the fluorinated ether composition    on the surface of the substrate.-   [12] A fluorinated ether compound, which is a compound represented    by the following formula (2):    A¹⁰—O—(R^(f1)O)_(m)—A²⁰   (2)-    wherein A¹⁰ is a C₁₋₂₀ perfluoroalkyl group, a group represented by    the following formula (g4-1), a group represented by the following    formula (g4-2) or a group represented by the following formula    (g4-3),    -   A²⁰ is a group represented by the following formula (g4-1), a        group represented by the following formula (g4-2) or a group        represented by the following formula (g4-3),    -   R^(f1) is a fluoroalkylene group,    -   m is an integer of from 2 to 500, and    -   (R^(f1)O)_(m) may consist of two or more types of R^(f1)O        differing in the number of carbon atoms:        —Q¹[—C(R¹¹⁰)_(b)(R¹²)_(3−b)]_(a)   (g4-1)        —Q¹[—N(R¹¹⁰)₂]_(a)   (g4-2)        —Q¹[—Z(R¹¹⁰)_(n)]_(a)   (_(g)4-3)-    wherein Q¹ is a a+1 valent organic group (provided that the    terminal bonded to the terminal oxygen atom of O(R^(f1)O)_(m) is CF₂    or CHF),    -   Z is a group having a n+1 valent cyclic structure having a        carbon atom or a nitrogen atom to which Q¹ is directly bonded        and a carbon atom or a nitrogen atom to which R¹¹⁰ is directly        bonded,    -   R¹¹⁰ is a group represented by the following formula (g5),    -   R¹² is a hydrogen atom, a halogen atom, a hydroxy group or a        monovalent organic group,    -   a is an integer of from 1 to 3,    -   b is 2 or 3,    -   n is an integer of at least 2,    -   when a is at least 2, the a [—C(R¹¹⁰)_(b)(R¹²)_(3−b)] may be the        same or different, the a [—N(R¹¹⁰)₂] may be the same or        different, and the a [—Z(R¹¹⁰)_(n)] may be the same or        different, and    -   a plurality of R¹¹⁰ may be the same or different;        —Q²—Si(R²¹⁰)_(c)(R²²)_(d)(R²³)_(e)   (g5)-    wherein Q² is a single bond or a bivalent organic group,    -   R²¹⁰ is a group represented by the following formula (g6),    -   R²² is an alkyl group,    -   R²³ is a hydrolyzable group or a hydroxy group,    -   c, d and e are each independently an integer of from 0 to 3,    -   c+d+e is 3,    -   in at least one R¹¹⁰ among a plurality of R¹¹⁰ in each of A¹⁰        and A²⁰, c is 2 or 3,    -   when c is at least 2, the c R²¹⁰ may be the same or different,    -   when d is at least 2, the d R²² may be the same or different,    -   when e is at least 2, the e R²³ may be the same or different;        —Q³⁰—CH═CH₂   (g6)    -   wherein Q³⁰ is a single bond or a bivalent organic group.-   [13] The fluorinated ether compound according to [12], wherein A¹⁰    is a C₁₋₂₀ perfluoroalkyl group.

Advantageous Effects of Invention

By the fluorinated ether compound of the present invention, it ispossible to form a surface layer excellent in fingerprint stainremovability and abrasion resistance as before and more excellent inlight resistance than ever.

By the fluorinated ether composition of the present invention, it ispossible to form a surface layer excellent in fingerprint stainremovability and abrasion resistance as before and more excellent inlight resistance than ever.

By the coating liquid of the present invention, it is possible to form asurface layer excellent in fingerprint stain removability and abrasionresistance as before and more excellent in light resistance than ever.

The article of the present invention has a surface layer excellent infingerprint stain removability and abrasion resistance as before andmore excellent in light resistance than ever.

According to the method for producing an article of the presentinvention, it is possible to produce an article having a surface layerexcellent in fingerprint stain removability and abrasion resistance asbefore and more excellent in light resistance than ever.

According to another embodiment, the fluorinated ether compound of thepresent invention is useful as an intermediate of the fluorinated ethercompound suitably used for a surface treatment agent.

DESCRIPTION OF EMBODIMENTS

In this specification, a compound represented by the formula (1) will bereferred to as compound (1). Compounds represented by other formulaewill be referred to in the same manner.

Further, a group represented by the formula (g1) will be referred to asgroup (g1). Groups represented by other formulae will be referred to inthe same manner.

The chemical formula of the oxyfluoroalkylene unit is represented sothat its oxygen atom is described on the right-side of thefluoroalkylene group.

In this specification, meanings of the following terms are as follows.

A “hydrolyzable silyl group” means a group capable of forming a silanolgroup (Si—OH) by being hydrolyzed. The hydrolyzable silyl group may, forexample, be Si(R³¹)_(3−g)(R³²)_(g) in the formula (g3).

A “surface layer” means a layer formed on the surface of a substrate.

The “number average molecular weight” of the fluorinated ether compoundis calculated by obtaining the number (average value) ofoxyperfluoroalkylene groups on the basis of the terminal group, by¹H-NMR and ¹⁹F-NMR. The terminal group may, for example, be A¹ in theformula (1) or Si(R³¹)_(3−g)(R³²)_(g) in the formula (g3).

[Fluorinated Ether Compound]

A fluorinated ether compound of the present invention is a compound (1):A¹—O—(R^(f1)O)_(m)—A²   (1)wherein A¹ is a C₁₋₂₀ perfluoroalkyl group, group (g1-1), group (g1-2)or group (g1-3),

-   -   A² is group (g1-1), group (g1-2) or group (g1-3),    -   R^(f1) is a fluoroalkylene group,    -   m is an integer of from 2 to 500, and    -   (R^(f1)O)_(m) may consist of two or more types of R^(f1)O        differing in the number of carbon atoms:        —Q¹[—C(R¹¹)_(b)(R¹²)_(3−b)]_(a)   (g1-1)        —Q¹[—N(R¹¹)₂]_(a)   (g1-2)        —Q¹[—Z(R¹¹)_(n)]_(a)   (g1-3)        wherein Q¹ is a a+1 valent organic group (provided that the        terminal bonded to the terminal oxygen atom of O(R^(f1)O)_(m) is        CF₂ or CHF),    -   Z is a group having a n+1 valent cyclic structure having a        carbon atom or a nitrogen atom to which Q¹ is directly bonded        and a carbon atom or a nitrogen atom to which R¹¹ is directly        bonded,    -   R¹¹ is group (g2),    -   R¹² is a hydrogen atom, a halogen atom, a hydroxy group or a        monovalent organic group,    -   a is an integer of from 1 to 3,    -   b is 2 or 3,    -   n is an integer of at least 2,    -   when a is at least 2, the a [—C(R¹¹)_(b)(R¹²)_(3−b)] may be the        same or different, the a [—N(R¹¹)₂] may be the same or        different, and the a [—Z(R¹¹)_(n)] may be the same or different,        and    -   a plurality of R¹¹ may be the same or different;        —Q²—Si(R²¹)_(c)(R²²)_(d)(R₂₃)_(e)   (g2)        wherein Q² is a single bond or a bivalent organic group,    -   R²¹ is group (g3),    -   R²² is an alkyl group,    -   R²³ is a hydrolyzable group or a hydroxy group,    -   c, d and e are each independently an integer of from 0 to 3,    -   c+d+e is 3,    -   in at least one R¹¹ among a plurality of R¹¹ in each of A¹ and        A², c is 2 or 3,    -   when c is at least 2, the c R²¹ may be the same or different,    -   when d is at least 2, the d R²² may be the same or different,    -   when e is at least 2, the e R²³ may be the same or different;        —Q³—Si(R³¹)_(3−g)(R³²)_(g)   (g3)    -   wherein Q³ is a bivalent organic group,    -   R³¹ is an alkyl group,    -   R³² is a hydrolyzable group or a hydroxy group,    -   g is an integer of from 1 to 3,    -   when g is 1, the two R³¹ may be the same or different, and    -   when g is at least 2, the g R³² may be the same or different.

A¹ is preferably a C₁₋₂₀ perfluoroalkyl group, in that the resultingsurface layer will be more excellent in lubricity and abrasionresistance. The compound (1) wherein A¹ is a perfluoroalkyl group has,since A¹ has CF₃— at its terminal, CF₃— at one terminal, and has ahydrolyzable silyl group or a silanol group at the other terminal.According to the compound (1) wherein one terminal is CF₃— and the otherterminal is a hydrolyzable silyl group or a silanol group, a surfacelayer having a low surface energy can be formed, whereby the surfacelayer is more excellent in lubricity and abrasion resistance as comparedwith that formed of the compound (1) having a hydrolyzable silyl groupor a silanol group at both terminals (the compound (1) wherein A¹ is anyof the group (g1) to the group (g3)).

The number of carbon atoms in the perfluoroalkyl group as A¹ ispreferably from 1 to 10, more preferably from 1 to 6, particularlypreferably from 1 to 3, in that the surface layer formed of the compound(1) will be more excellent in lubricity and abrasion resistance.

The number of carbon atoms in R^(f1) is preferably from 1 to 6, in thatthe surface layer will be more excellent in abrasion resistance andfingerprint stain removability.

R^(f1) is preferably a linear fluoroalkylene group in that the surfacelayer will be more excellent in abrasion resistance and lubricity.

R^(f1) is preferably a perfluoroalkylene group in that the surface layerwill be more excellent in abrasion resistance and lubricity.

The proportion of the perfluoroalkylene group to the entire R^(f1) ispreferably at least 60 mol %, more preferably at least 80 mol %,particularly preferably 100 mol %, in that the surface layer will bemore excellent in abrasion resistance and lubricity.

m is preferably an integer of from 2 to 200, more preferably an integerof from 5 to 150, particularly preferably an integer of from 10 to 100.When m is at least the lower limit value of the above range, the surfacelayer will be more excellent in water/oil repellency. When m is at mostthe upper limit value of the above range, the surface layer will be moreexcellent in abrasion resistance. That is, if the number averagemolecular weight of the compound (1) is too high, the number ofhydrolyzable silyl groups or silanol groups present per unit molecularweight decreases, and the abrasion resistance of the surface layer willbe lowered.

In (R^(f1)O)_(m), when at least two types of R^(f1)O are present, thebonding order of the respective R^(f1)O is not limited. For example,when CF₂O and CF₂CF₂O are present, such CF₂O and CF₂CF₂O may be arrangedrandomly, alternately or in block.

At least two types of R^(f1)O being present means that at least twotypes of R^(f1)O differing in the number of carbon atoms are present, atleast two types of R^(f1)O differing in the number of hydrogen atoms arepresent, at least two types of R^(f1)O differing in the positions ofhydrogen atoms are present, and at least two types of R^(f1)O differingin whether side chains are present or not or in the type of side chains(e.g. the number of side chains, the number of carbon atoms in the sidechain) even having the same number of carbon atoms, are present.

With respect to arrangement of at least two types of R^(f1)O, forexample, a structure represented by {(CF₂O)_(m1)(CF₂CF₂O)_(m2)}indicates that ml pieces of (CF₂O) and m2 pieces of (CF₂CF₂O) arerandomly arranged. Further, a structure represented by(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(m5) indicates that m5 pieces of (CF₂CF₂O) andm5 pieces of (CF₂CF₂CF₂CF₂O) are alternately arranged.

As (R^(f1)O)_(m), preferred is (R^(f1)O)_(m) having the followingstructure in at least a part thereof.{(CF₂O)_(m1)(CF₂CF₂O)_(m2)}(CF₂CF₂O)_(m3)(CF₂CF₂CF₂O)_(m4)(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(m5)(CF₂CF₂CF₂CF₂CF₂O)_(m6)(CF₂O)_(m7)(CF₂CF₂CF₂CF₂CF₂O)_(m6)(CF₂CF₂O)_(m7)(CF₂CF₂CF₂CF₂CF₂CF₂O)_(m6)(CF₂O)_(m7)(CF₂CF₂CF₂CF₂CF₂CF₂O)_(m6)(CF₂CF₂O)_(m7)(CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(m8)(CF₂CF₂CF₂CF₂CF₂O—CF₂CF₂O)_(m8)(CF₂CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(m8)(CF₂CF₂CF₂CF₂CF₂CF₂O—CF₂CF₂O)_(m8)(CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(m8)(CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(m8)(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(m8)(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(m8)wherein m1 is an integer of at least 1, m2 is an integer of at least 1,m1+m2 is an integer of from 2 to 500, m3 and m4 are each an integer offrom 2 to 500, m5 is an integer of from 1 to 250, m6 and m7 are each aninteger of at least 1, m6+m7 is an integer of from 2 to 500, and m8 isan integer of from 1 to 250.

(R^(f1)O)_(m) is preferably as follows, in view of easy production ofthe compound (1).{(CF₂O)_(m1)(CF₂CF₂O)_(m2)},(CF₂CF₂CF₂O)_(m4),(CF₂CF₂O)₂{(CF₂O)_(m1)(CF₂CF₂O)_(m2-2)},(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(m5-1)CF₂CF₂O,(CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(m8),(CF₂CF₂CF₂CF₂CF₂CF₂O—CF₂O)_(m8),(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂O)_(m8-1)CF₂CF₂O,(CF₂CF₂O—CF₂CF₂CF₂CF₂CF₂CF₂O)_(m8-1)CF₂CF₂O,wherein m2, m5 and m8 are selected so that m2-2, m5-1 and m8-1 are aninteger of at least 1.

a is preferably from 1 to 2, particularly preferably 1, in that thecompound (1) is easily produced, the surface of the substrate isuniformly coated with the compound (1), and the obtainable surface layerwill be excellent in physical properties.

Q¹ may have a bond selected from the group consisting of —C(O)NR—,—C(O)O—, —C(O)—, —O—, —NR—, —S—, —NHC(O)O—, —NHC(O)NR—, —SO₂NR— andSi(R)₂— wherein R is a hydrogen atom, a C₁₋₆ alkyl group or a phenylgroup (hereinafter referred to as “bond B”). The bond B is preferably abond selected from the group consisting of —C(O)NR—, —C(O)— and Si(R)₂—in that the surface layer will be more excellent in light resistance andchemical resistance.

The organic group as Q¹ is, in that the surface layer will be moreexcellent in light resistance and chemical resistance, preferably afluorohydrocarbon group, a combination of a fluorohydrocarbon group andthe bond B or a combination of a fluorohydrocarbon group, the bond B anda hydrocarbon group, particularly preferably a fluorohydrocarbon group.The number of carbon atoms in Q¹ is preferably from 1 to 10, morepreferably from 1 to 6, particularly preferably from 1 to 4.

When a is 1, Q¹ is, in that the compound (1) is easily produced and theresulting surface layer will be more excellent in light resistance andchemical resistance, preferably group (g11), group (g12), group (g13) orgroup (g14).—R^(f2)—Q¹¹—  (g11)—R^(f2)—C(O)NR—Q¹¹—  (g12)—R^(f2)—C(O)CH₂C(O)—Q¹¹—  (g13)—R^(f2)—C(O)—Q¹¹—  (g14)wherein R^(f2) is a fluoroalkylene group (having at least one fluorineatom bonded to the terminal carbon atom on the Q¹¹ side and to theterminal carbon atom on the O(R^(f1)O)_(m) side), Q¹¹ is a single bondor an alkylene group, and R is a hydrogen atom, a C₁₋₆ alkyl group or aphenyl group. The R^(f2) side is bonded to the terminal oxygen atom ofO(R^(f1)O)_(m).

The number of carbon atoms in R^(f2) is preferably from 1 to 8, morepreferably from 1 to 6, particularly preferably from 1 to 5, in that theresulting surface layer will be more excellent in abrasion resistanceand fingerprint stain removability.

R^(f2) is preferably a linear fluoroalkylene group in that the surfacelayer will be more excellent in abrasion resistance and lubricity.

R^(f2) is preferably a perfluoroalkylene group in that the surface layerwill be more excellent in abrasion resistance and lubricity.

The structure of R^(f2) depends on the raw materials and the method forpreparing the compound (1).

The number of carbon atoms in the alkylene group as Q¹¹ is preferablyfrom 1 to 6.

R¹² may have a bond B.

The organic group as R¹² is, in that the surface layer will be moreexcellent in light resistance and chemical resistance, preferably ahydrocarbon group, a fluorohydrocarbon group or a combination of ahydrocarbon group and the bond B, particularly preferably a hydrocarbongroup. The hydrocarbon group is preferably a saturated aliphatichydrocarbon group, an aromatic hydrocarbon group or a combinationthereof, particularly preferably an alkyl group. The number of carbonatoms in R¹² is preferably from 1 to 6, more preferably from 1 to 4,particularly preferably from 1 to 3.

The cyclic structure as Z is, in that the compound (1) is easilyproduced, and the resulting surface layer will be more excellent inabrasion resistance, light resistance and chemical resistance,preferably a cyclic structure selected from the group consisting of a 3-to 8-membered alicyclic ring, a 3- to 8-membered aromatic ring, a 3- to8-membered heterocyclic ring, and a condensed ring comprising two ormore of such rings, particularly preferably the following cyclicstructures.

The cyclic structure in Z may have a substituent such as a halogen atom,an alkyl group (which may have an etheric oxygen atom between carbonatoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxygroup or an oxo group (═O). Since Q¹ and R¹¹ are directly bonded to thecyclic structure as Z, it will not happen that an alkylene group forexample is bonded to the cyclic structure and Q¹ or R¹¹ is bonded to thealkylene group.

n is preferably from 2 to 6, more preferably from 2 to 4, particularlypreferably from 2 to 3, whereby the compound (1) is easily produced andthe resulting surface layer will be more excellent in abrasionresistance, light resistance and chemical resistance. When n is at least2, the compound (1) will be firmly bonded to the surface of thesubstrate, whereby the surface layer will be more excellent in abrasionresistance, light resistance and chemical resistance. When n is at most6, the raw materials will be easily available, and the compound (1) iseasily produced. Further, the terminal on the hydrolyzable silyl groupside of the compound (1) will not be bulky, and the density of thecompound (1) on the surface of the substrate is relatively high and as aresult, the surface layer will be more excellent in abrasion resistance,light resistance and chemical resistance.

Q² may have the bond B.

The organic group as Q² is, in that the resulting surface layer will bemore excellent in light resistance and chemical resistance, preferably ahydrocarbon group, a fluorohydrocarbon group, a combination of ahydrocarbon group and the bond B, or a combination of afluorohydrocarbon group, the bond B and a hydrocarbon group,particularly preferably a hydrocarbon group. The hydrocarbon group ispreferably a saturated aliphatic hydrocarbon group, an aromatichydrocarbon group or a combination thereof, particularly preferably analkylene group. The number of carbon atoms in Q² is, in that the surfacelayer will be more excellent in light resistance and chemicalresistance, preferably from 1 to 10, more preferably from 1 to 6,particularly preferably from 1 to 4.

Q² is, in that the compound (1) is easily produced, and the resultingsurface layer will be more excellent in abrasion resistance, lightresistance and chemical resistance, preferably a single bond or a C₁₋₆alkylene group, particularly preferably a single bond or a C₁₋₄ alkylenegroup.

The number of carbon atoms in the alkyl group as R²² is preferably from1 to 6, more preferably from 1 to 3, particularly preferably from 1 to2. When the number of carbon atoms in the alkyl group as R²² is withinsuch a range, the compound (1) is easily produced.

The hydrolyzable group as R²³ is a group which becomes a hydroxy groupby hydrolysis reaction. That is, Si—R²³ becomes a silanol group (Si—OH)by hydrolysis reaction. Silanol groups will further be intermolecularlyreacted to form Si—O—Si bonds. Further, a silanol group will undergodehydration condensation reaction with a hydroxy group (substrate-OH) onthe surface of a substrate, to form a chemical bond (substrate-O—Si).

R²³ may, for example, be an alkoxy group, a halogen atom, an acyl groupor an isocyanate group. The alkoxy group is preferably a C₁₋₄ alkoxygroup. The halogen atom is preferably a chlorine atom.

R²³ is, in view of easy production of the compound (1), preferably analkoxy group or a halogen atom. R²³ is, since outgassing duringapplication will be less, and storage stability of the compound (1) willbe excellent, preferably a C₁₋₄ alkoxy group, and in a case where longterm storage stability of the compound (1) is required, particularlypreferably an ethoxy group, and in a case where the reaction time aftercoating should be short, particularly preferably a methoxy group.

Q³ may have the bond B.

The organic group as Q³ is, in that the resulting surface layer will bemore excellent in light resistance and chemical resistance, preferably ahydrocarbon group, or a combination of a hydrocarbon group and the bondB, particularly preferably a hydrocarbon group. The hydrocarbon group ispreferably a saturated aliphatic hydrocarbon group, an aromatichydrocarbon group, or a combination thereof, particularly preferably analkylene group. The number of carbon atoms in Q³ is, in that the surfacelayer will be more excellent in light resistance and chemicalresistance, preferably from 1 to 10, more preferably from 2 to 6,particularly preferably from 2 to 4.

Q³ is, in that the compound (1) is easily produced and the resultingsurface layer will be more excellent in abrasion resistance, lightresistance and chemical resistance, preferably a C₂₋₆ alkylene group,particularly preferably a C₂₋₄ alkylene group.

Particularly when a is 1, Q² is a single bond or a C₁₋₆ alkylene group,and Q³ is a C₂₋₆ alkylene group, it is considered that in the compound(1), suppression of oxidative destruction at the C—C bond branched fromthe carbon atom, and improvement in the strength of the Si—C bondbranched from the silicon atom, will be more effectively obtained, andthe resulting surface layer will be more excellent in abrasionresistance and light resistance.

Si(R³¹)_(3−g)(R³²)_(g) is a hydrolyzable silyl group.

The compound (1) has more than one hydrolyzable silyl groups at least atone terminal. The compound (1) having more than one hydrolyzable silylgroups at its terminal is firmly chemically bonded to the substrate,whereby the resulting surface layer will be excellent in abrasionresistance.

Further, the compound (1) preferably has hydrolyzable silyl groups atonly one terminal. The compound (1) having hydrolyzable silyl groupsonly at one terminal is less likely to aggregate, and is thereby capableof forming a surface layer excellent in outer appearance. Further, thesurface layer will be excellent in lubricity and abrasion resistance.

As R³¹, groups similar to R²² may be mentioned, and the preferredembodiment is also the same.

As R³², groups similar to R²³ may be mentioned, and the preferredembodiment is also the same.

g is preferably 2 or 3, particularly preferably 3. By the presence of aplurality of R³² in one hydrolyzable silyl group, the adhesion to asubstrate will be more firm.

As Si(R³¹)_(3−g)(R³²)_(g), Si(OCH₃)₃, SiCH₃(OCH₃)₂, Si(OCH₂CH₃)₃, SiCl₃,Si(OCOCH₃)₃ or Si(NCO)₃ is preferred. In view of handling efficiency inindustrial production, Si(OCH₃)₃ is particularly preferred.

The plurality of Si(R³¹)_(3−g)(R³²)_(g) in the compound (1) may be thesame or different. From the production efficiency of the compound (1),they are preferably the same group.

As the compound (1), for example, the following compounds may bementioned. The following compounds are preferred in that they areindustrially easily produced and are easily handled, and the resultingsurface layer will be more excellent in water/oil repellency, abrasionresistance, fingerprint stain removability, lubricity, chemicalresistance, light resistance and chemical resistance, and particularlyexcellent in light resistance.

wherein G is a polyfluoropolyether chain, that is,A—O—(R^(f1)O)_(m)—R^(f2)— (wherein A is a C₁₋₂₀ perfluoroalkyl group). Apreferred embodiment of G is a combination of the above preferred A¹,(R^(f1)O)_(m) and R^(f2).(Method for Producing Compound (1))

The compound (1) may be produced, for example, by a method of subjectingcompound (2) and HSi(R³¹)_(3−g)(R³²)_(g) to hydrosilylation.A¹⁰—O—(R^(f1)O)_(m)—A²⁰   (2)wherein A¹⁰ is a C₁₋₂₀ perfluoroalkyl group, group (g4-1), group (g4-2)or group (g4-3), and A²⁰ is group (g4-1), group (g4-2) or group (g4-3).—Q¹[—C(R¹¹⁰)_(b)(R¹²)_(3−b)]_(a)   (g4-1)—Q¹[—N(R¹¹⁰)₂]_(a)   (g4-2)—Q¹[—Z(R¹¹⁰)_(n)]_(a)   (g4-3)wherein R¹¹⁰ is group (g5), and when a is at least 2, the a[—C(R¹¹⁰)_(b)(R¹²)_(3−b)] may be the same or different, the a[—N(R¹¹⁰)₂] may be the same or different, the a [—Z(R¹¹⁰)_(n)] may bethe same or different, and a plurality of R¹¹⁰ may be the same ordifferent.—Q²—Si(R²¹⁰)_(c)(R²²)_(d)(R²³)_(e)   (g5)wherein R²¹⁰ is group (g6), and in at least one R¹¹⁰ among a pluralityof R¹¹⁰ in each of A¹⁰ and A²⁰, c is 2 or 3, and when c is at least 2,the c R²¹⁰ may be the same or different.—Q³⁰—CH═CH₂   (g6)wherein Q³⁰ is a single bond or a bivalent organic group.

(R^(f1)O)_(m), Q¹, Z, R¹², a, b, n, Q², R²², R²³, c, d and e are thesame as (R^(f1)O)_(m), Q¹, Z, R¹², a, b, n, Q², R²², R²³, c, d and e asdescribed for the compound (1), and the preferred embodiments are alsothe same.

A¹⁰ is, in that the resulting surface layer will be more excellent inlubricity and abrasion resistance, preferably a C₁₋₂₀ perfluoroalkylgroup.

The number of carbon atoms in the perfluoroalkyl group as A¹⁰ is, inthat the resulting surface layer will be more excellent in lubricity andabrasion resistance, preferably from 1 to 10, more preferably from 1 to6, particularly preferably from 1 to 3.

Q³⁰ may have the bond B.

The organic group as Q³⁰ is, in that the resulting surface layer will bemore excellent in light resistance and chemical resistance, preferably ahydrocarbon group, or a combination of a hydrocarbon group and the bondB, particularly preferably a hydrocarbon group. The hydrocarbon group ispreferably a saturated aliphatic hydrocarbon group, an aromatichydrocarbon group or a combination thereof, particularly preferably analkylene group. The number of carbon atoms in Q³⁰ is, in that theresulting surface layer will be more excellent in light resistance andchemical resistance, preferably from 1 to 8, more preferably from 2 to4, particularly preferably from 1 to 2.

Q³⁰ is, in that the compound (2) is easily produced and the resultingsurface layer will be more excellent in abrasion resistance, lightresistance and chemical resistance, preferably a single bond or a C₁₋₄alkylene group, particularly preferably a single bond or a C₁₋₂ alkylenegroup.

Q³⁰—CH═CH₂ becomes Q³ in the group (g3) after the hydrosilylation.

(Method for Producing Compound (2))

(i) The compound (2) may be produced, for example, as follows.

Compound (4) and a Grignard reagent (CH₂═CH—Q³⁰—MgBr) are reacted toobtain compound (2a).A—O—(R^(f1)O)_(m)—Q¹—C[—Q²—Si(R²³)_(c)(R²²)_(d)]_(b)(R¹²)_(3−b)   (4)A—O—(R^(f1)O)_(m)—Q¹—C[—Q²—Si(—Q³⁰—CH═CH₂)_(c)(R²²)_(d)]_(b)(R¹²)_(3−b)  (2a)wherein A is a C₁₋₂₀ perfluoroalkyl group.

(R^(f1)O)_(m), Q¹, R¹², b, Q², R²², R²³, c, d and Q³⁰ are the same as(R^(f1)O)_(m) , Q¹, R¹², b, Q², R²², R²³, c, d and Q³⁰ as described forthe compounds (1) and (2), and the preferred embodiments are also thesame.

The compound (4) may be produced, for example, by the method disclosedin Patent Document 1 (b=3), JP-A-2015-199906 (b=2, R¹²=hydroxy group),or JP-A-2016-204656 (b=3).

(ii) Further, the compound (2) may be produced, for example, as follows.

Compound (6) and CH₂═CH—Si(R²³)_(c)R²² _(d) are reacted to obtaincompound (7).A—O—(R^(f1)O)_(m)—R^(f2)—I   (6)A—O—(R^(f1)O)_(m)—R^(f2)—CH₂—CHI—Si(R²³)_(c)(R²²)_(d)   (7)

The compound (7) and a Grignard reagent (CH₂═CH—Q³⁰—MgBr) are reacted toobtain compound (2b).A—O—(R^(f1)O)_(m)—R^(f2)—CH₂—CH(—Q³⁰—CH═CH₂)[—Si(—Q³⁰—CH═CH₂)_(c)(R²²)_(d)]  (2b)wherein A is a C₁₋₂₀ perfluoroalkyl group.

(R^(f1)O)_(m), R^(f2), R²², c, d and Q³⁰ are the same as (R^(f1)O)_(m),R^(f2), R²², c, d and Q³⁰ as described for the compounds (1) and (2),and the preferred embodiments are also the same.

The compound (6) may be produced, for example, by the method disclosedin WO2009/008380, WO2013/121984 or WO2013/121986.

(iii) Further, the compound (2) may be produced, for example, asfollows.

Compound (8) and a Grignard reagent (CH₂═CH—Q³⁰—MgBr) are reacted toobtain compound (2c).A—O—(R^(f1)O)_(m)—Q¹—N[—Q²—Si(R²³)_(c)(R²²)_(d)]₂   (8)A—O—(R^(f1)O)_(m)—Q¹—N[—Q²—Si(—Q³⁰—CH═CH₂)_(c)(R²²)_(d)]₂   (2c)wherein A is a C₁₋₂₀ perfluoroalkyl group.

(R^(f1)O)_(m), Q¹, Q², R²², R²³, c, d and Q³⁰ are the same as(R^(f1)O)_(m), Q¹, Q², R²², R²³, c, d and Q³⁰ as described for thecompounds (1) and (2), and the preferred embodiments are also the same.

The compound (8) may be produced, for example, by the method disclosedin Patent Document 2.

The above-described compound (1) is capable of forming a surface layerexcellent in fingerprint stain removability, abrasion resistance andlight resistance, from the following reasons.

The compound (1), which has (R^(f1)O)_(m), has a high fluorine atomcontent. Therefore, the compound (1) is capable of forming a surfacelayer excellent in abrasion resistance and fingerprint stainremovability.

The compound (1) has at least two R¹¹ bonded to a carbon atom or anitrogen atom, and in at least one R¹¹ among a plurality of R¹¹ (thatis, a plurality of Q²—Si(R²¹)_(c)(R²²)_(d)(R²³)_(e)), c is 2 or 3. Thus,more than one hydrolyzable silyl groups are introduced via two-stagebranches i.e. a branch by a carbon atom or a nitrogen atom at theterminal and a subsequent branch by a silicon atom. Accordingly, it ispossible to form a surface layer excellent in fingerprint stainremovability and abrasion resistance as before and more excellent inlight resistance than ever.

Here, for example, in a case where the compound (1) has the group(g1-1), the compound (1) is considered to have a branch by a carbon atomby —C(R¹¹)_(b)(R¹²)_(3−b) in the group (g1-1). Further, the compound (1)is considered to have a branch by the subsequent silicon atom by—Q²—Si(R²¹)_(c)(R²²)_(d)(R²³)_(e) in R¹¹. The same applies to a casewhere the compound (1) has the group (g1-2) or the group (g1-3), or acase where two or more groups of at least one type selected from thegroups (g1-1) to (g1-3).

The reason why a surface layer excellent in fingerprint stainremovability and abrasion resistance as before and more excellent inlight resistance than ever can be formed by the compound (1) having abranch by a carbon atom or a nitrogen atom and a branch by thesubsequent silicon atom, the following reason is considered.

A surface layer excellent in abrasion resistance can be formed by afluorinated ether compound having a C—C bond branched from a carbonatom, since the C—C bond branched from the carbon atom is strong.However, the fluorinated ether compound having the C—C bond branchedfrom a carbon atom gradually undergoes oxidative destruction whenexposed to sunlight in air for a long period of time, and iscomplicatedly decomposed by a hydrogen atom being withdrawn by radicalsfor example at a methine structure moiety. Even when the branched moietyby the carbon atom is a quaternary carbon atom, the carbon radicalformed by cleavage at the C—C bond is stable, originating from which thecompound is decomposed. The branch by a nitrogen atom is the same as thebranch by the carbon atom.

It is considered that in one molecule, by introducing the branch by asilicon atom subsequent to the branch by the carbon atom or the nitrogenatom, the Si—C bond (Si—C bond branched from the silicon atom)considered to be more stable against oxidation than the C—C bondbranched from the carbon atom can suppress oxidative destruction andfurther, by the interaction between the Si—C bond branched from thesilicon atom and the C—C bond branched from the carbon atom, oxidativedestruction at the C—C bond branched from the carbon atom can also besuppressed. It is also considered that by the interaction between theSi—C bond branched from the silicon atom and the C—C bond branched fromthe carbon atom, the strength of the Si—C bond branched from the siliconatom can also be kept in a favorable state.

Accordingly, by incorporating the two types of branched structures whichare chemically and physically strong but are different from each other,into one molecule by the embodiment of the present invention, a surfacelayer excellent in fingerprint stain removability and abrasionresistance as before and more excellent in light resistance than evercan be formed. Accordingly, a surface layer formed of the compound (1)of the present invention can tolerate a severe evaluation method ofconducting light resistance test and further conducting abrasionresistance test.

[Fluorinated Ether Composition]

The fluorinated ether composition of the present invention (hereinaftersometimes referred to as “the present composition”) comprises at leastone type of the compound (1) and other fluorinated ether compound.

As other fluorinated ether compound, a fluorinated ether compound formedas a by-product during production of the compound (1) (hereinaftersometimes referred to as “by-product fluorinated ether compound”) and aknown fluorinated ether compound used in the same applications as thecompound (1) may, for example, be mentioned.

Other fluorinated ether compound is preferably one unlikely to impairthe properties of the compound (1).

As the by-product fluorinated ether compound, unreacted compounds (2),(4), (6), (7) and the like, and fluorinated ether compounds formedthrough isomerization of some of the allyl groups into an inner olefinaccompanying hydrosilylation during the production of the compound (1)may, for example, be mentioned.

As the known fluorinated ether compound, a commercially availablefluorinated ether compound may, for example, be mentioned. In a casewhere the present composition contains a known fluorinated ethercompound, it may have new effects such as compensation for theproperties of the compound (1).

In the present composition, the content of the compound (1) ispreferably at least 60 mass % and less than 100 mass %, more preferablyat least 70 mass % and less than 100 mass %, particularly preferably atleast 80 mass % and less than 100 mass %, to the total amount of thecompound (1) and other fluorinated ether compound.

The total content of the compound (1) and other fluorinated ethercompound in the present composition is preferably from 80 to 100 mass %,particularly preferably from 85 to 100 mass % to the presentcomposition.

When the content of the compound (1) and the content of otherfluorinated ether compound are within the above ranges, the surfacelayer will be more excellent in initial water/oil repellency, abrasionresistance, fingerprint stain removability, light resistance andchemical resistance.

The present composition may contain a component other than the compound(1) and other fluorinated ether compound within a range not to impairthe effects of the present invention.

Other component may, for example, be a by-product formed duringproduction of the compound (1) or the known fluorinated ether compound(excluding the by-product fluorinated ether compound) or a compoundinevitable in production such as an unreacted raw material.

Further, additives such as an acid catalyst or a basic catalyst topromote hydrolysis and condensation reaction of the hydrolyzable silylgroup may be mentioned. The acid catalyst may, for example, behydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoricacid, sulfonic acid, methanesulfonic acid or p-toluenesulfonic acid. Thebasic catalyst may, for example, be sodium hydroxide, potassiumhydroxide or ammonia.

The content of other component is preferably from 0 to 10 mass %,particularly preferably from 0 to 1 mass % to the present composition.

[Coating Liquid]

The coating liquid of the present invention (hereinafter sometimesreferred to as “the present coating liquid”) comprises the compound (1)or the present composition, and a liquid medium. The present coatingliquid may be a solution or a dispersion.

The liquid medium is preferably an organic solvent. The organic solventmay be a fluorinated organic solvent, may be a non-fluorinated organicsolvent, or may contain both solvents.

The fluorinated organic solvent may, for example, be a fluorinatedalkane, a fluorinated aromatic compound, a fluoroalkyl ether, afluorinated alkylamine or a fluoroalcohol.

The fluorinated alkane is preferably a C₄₋₈ compound. Commerciallyavailable products may, for example, be C₆F₁₃H (manufactured by AGCInc., ASAHIKLIN (registered trademark) AC-2000), C₆F₁₃C₂H₅ (manufacturedby AGC Inc., ASAHIKLIN (registered trademark) AC-6000), andC₂F₅CHFCHFCF₃ (manufactured by Chemours, Vertrel (registered trademark)XF).

The fluorinated aromatic compound may, for example, behexafluorobenzene, trifluoromethylbenzene, perfluorotoluene orbis(trifluoromethyl)benzene.

The fluoroalkyl ether is preferably a C₄₋₁₂ compound. Commerciallyavailable products may, for example, be CF₃CH₂OCF₂CF₂H (manufactured byAGC Inc., ASAHIKLIN (registered trademark) AE-3000), C₄F₉OCH₃(manufactured by 3M, Novec (registered trademark) 7100), C₄F₉OC₂H₅(manufactured by 3M, Novec (registered trademark) 7200), andC₂F₅CF(OCH₃)C₃F₇ (manufactured by 3M, Novec (registered trademark)7300).

The fluorinated alkylamine may, for example, be perfluorotripropylamineor perfluorotributylamine,

The fluoroalcohol may, for example, be 2,2,3,3-tetrafluoropropanol,2,2,2-trifluoroethanol or hexafluoroisopropanol.

The non-fluorinated organic solvent is preferably a compound consistingsolely of hydrogen atoms and carbon atoms, or a compound consistingsolely of hydrogen atoms, carbon atoms and oxygen atoms, and may be ahydrocarbon, an alcohol, a ketone, an ether, or an ester.

The liquid medium may be a mixed medium having two or more types mixed.

The content of the compound (1) or the present composition is preferablyfrom 0.001 to 10 mass %, particularly preferably from 0.01 to 1 mass %to the present coating liquid.

The content of the liquid medium is preferably from 90 to 99.999 mass %,particularly preferably from 99 to 99.99 mass % in the present coatingliquid.

[Article]

The article of the present invention (hereinafter sometimes referred toas “the present article”) comprises a substrate and a surface layerformed of the compound (1) or the present composition on a surface ofthe substrate.

The surface layer contains the compound (1) in a state where some or allof hydrolyzable silyl groups in the compound (1) are hydrolyzed andsubjected to dehydration condensation reaction.

The thickness of the surface layer is preferably from 1 to 100 nm,particularly preferably from 1 to 50 nm. When the thickness of thesurface layer is at least 1 nm, the effect by the surface treatment islikely to be sufficiently obtained. When the thickness of the surfacelayer is at most 100 nm, utilization efficiency will be high. Thethickness of the surface layer can be calculated from an oscillationperiod of an interference pattern of reflected X-ray, obtained by X-rayreflectance method using an X-ray diffractometer for thin film analysis(manufactured by Rigaku Corporation, ATX-G).

The substrate may be a substrate which is desired to have water/oilrepellency imparted. The material of the substrate may, for example, bea metal, a resin, glass, sapphire, ceramic, stone or a compositematerial thereof. The glass may be chemically tempered. The substratemay have a primer film such as a SiO₂ film formed on its surface.

As the substrate, a substrate for a touch panel, a substrate for displayor a spectacle lens is preferred, and a substrate for a touch panel isparticularly preferred. As the material of a substrate for a touchpanel, glass or a transparent resin is preferred.

[Method for Producing Article]

The present article may be produced, for example, by the followingmethod.

-   -   A method of treating the surface of a substrate by dry coating        method using the compound (1) or the present composition, to        form a surface layer formed of the compound (1) or the present        composition on the surface of the substrate.    -   A method of applying the present coating liquid to the surface        of a substrate by wet coating method, followed by drying to form        a surface layer formed of the compound (1) or the present        composition on the surface of the substrate.

As the dry coating method, a method such as vacuum deposition, CVD orsputtering may be mentioned. As the dry coating method, with a view tosuppressing decomposition of the compound (1) and from the viewpoint ofsimplicity of apparatus, vacuum deposition method is preferred. At thetime of vacuum deposition, a pelletized material having a metal porousproduct of iron, steel of the like impregnated with the compound (1) orthe present composition may be used. A pelletized material impregnatedwith the compound (1) or the present composition, obtained byimpregnating a metal porous product of iron, steel of the like with thepresent coating liquid and drying the liquid medium, may be used.

The wet coating method may, for example, be a spin coating method, awipe coating method, a spray coating method, a squeegee coating method,a dip coating method, a die coating method, an ink-jet method, a flowcoating method, a roll coating method, a casting method, aLangmuir-Blodgett method, or a gravure coating method.

EXAMPLES

Now, the present invention will be described in further detail withreference to Examples, but the present invention is not limited to theseExamples. Hereinafter, “%” is “mass %” unless otherwise specified. Ex. 4and 5 are Examples of the present invention, and Ex. 6 is a ComparativeExample.

Ex. 1 Ex. 1-1

Compound (3-1) was obtained in accordance with the method disclosed inEx. 11-1 to 11-2 in WO2017/038830.

Mean value of x: 13, number average molecular weight of compound (3-1):4,800.

Ex. 1-2

Into a 50 mL eggplant flask, 10 g of compound (3-1) obtained in Ex. 1-1,0.9 g of methyldimethoxysilane, 0.009 g of aniline, 10 g of C₆F₁₃C₂H₅(manufactured by AGC Inc., ASAHIKLIN (registered trademark) AC-6000),and 0.033 g of a platinum/divinyltetramethyldisiloxane complex were put,followed by stirring at 25° C. overnight. The mixture was concentratedto obtain 10 g of compound (4-1).

NMR spectrum of compound (4-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: tetramethylsilane (TMS)) δ(ppm): 3.9(18H), 3.3(2H), 1.1 to 2.0(12H), 0.5 to 1.0(6H), 0(9H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −55.2(3F),−82.1(54F), −88.1(54F), −90.2(2F), −119.6(2F), −125.4(52F), −126.2(2F).

Mean value of x: 13.

Ex. 1-3

Into a 200 mL three-necked flask, the system in which was replaced withnitrogen, 30 mL of a 0.7 mol/L ether solution of allyl magnesium bromideand 30 mL of dichloropentafloropropane (manufactured by AGC Inc.,AK-225) were put, followed by stirring at 25° C. 10 g of the compound(4-1) obtained in Ex. 1-2 diluted with 50 mL of AK-225 was put into thethree-necked flask little by little, followed by stirring overnight. Theobtained crude product was quenched with a 1 mol/L hydrochloric acidaqueous solution, followed by liquid separation with AK-225, and theresulting organic layer was concentrated and purified by silica gelcolumn chromatography to obtain 9.3 g of compound (2-1).

NMR spectrum of compound (2-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 6.0(6H),5.0(12H), 3.3(2H), 1.1 to 2.0(24H), 0.5 to 1.0(6H), 0.0(9H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −55.2(3F),−82.1(54F), −88.1(54F), −90.2(2F), −119.6(2F), −125.4(52F), −126.2(2F).

Mean value of x: 13.

Ex. 1-4

Into a 50 mL eggplant flask, 9.0 g of the compound (2-1) obtained in Ex.1-3, 2.20 g of trimethoxysilane, 0.0220 g of aniline, 9.0 g of AC-6000and 0.03 g of a platinum/divinyltetramethyldisiloxane complex were put,followed by stirring at 25° C. overnight. The mixture was concentratedto obtain 9.0 g of compound (1-1).

NMR spectrum of compound (1-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.9(18H),3.4(2H), 1.1 to 2.0(24H), 0.5 to 1.0(30H), 0.0(9H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −55.2(3F),−82.1(54F), −88.1(54F), −90.2(2F), −119.6(2F), −125.4(52F), −126.2(2F).

Mean value of x: 13.

Ex. 2 Ex. 2-1

Compound (5-1) was obtained in accordance with the method disclosed inEx. 11-1 to 11-3 in WO2013/121984.CF₃—O—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x)CF₂CF₂O—CF₂CF₂CF₂—CF₂OC(O)CF(CF₃)OCF₂CF₂CF₃  (5-1)

Mean value of unit number x: 13, number average molecular weight ofcompound (5-1): 5,050.

Ex. 2-2

Into a 500 mL eggplant flask light-shielded with an aluminum foil, 5.8 gof sodium pyrithione and 100 mL of 1,3-bistrifluoromethylbenzene(manufactured by AGC SEIMI CHEMICAL CO., LTD., SR-solvent) were put,followed by stirring under cooling in an ice bath. Then, 50.0 g of thecompound (5-1) obtained in Ex. 2-1 was slowly added, followed bystirring for 2 hours under cooling in an ice bath. Then, 12.0 g ofiodine and 1.8 g of 2,2-azobis(2-methylbutylonitrile) (manufactured byWako Pure Chemical Industries, Ltd., V-59) were put, the aluminum foilfor light shielding was removed, followed by stirring at 85° C.overnight. The temperature was returned to 25° C., methanol was added,followed by sufficient stirring, and AC-6000 was put for separation intotwo layers, the lower layer was recovered, and the solvent was distilledoff. The obtained crude product was purified by silica gel columnchromatography to obtain 39.8 g of compound (6-1).CF₃—O—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x)CF₂CF₂O—CF₂CF₂CF₂—I   (6-1)

NMR spectrum of compound (6-1):

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −55(3F),−58(2F), −83(50F), −88(52F), −90(2F), −116(2F), −125(52F).

Mean value of x: 13.

Ex. 2-3

Into a 50 mL eggplant flask, 10 g of the compound (6-1) obtained in Ex.2-2, 2.0 g of dichloromethylvinylsilane (manufactured by TCI), 30 mL ofClCF₂CFClCF₂OCF₂CF₂Cl (CFE-419) and 36 mg of PERBUTYL PV (manufacturedby NOF CORPORATION) were put, followed by stirring at 65° C. overnight.The reaction temperature was returned to 25° C., and the solvent wasdistilled off to obtain 9.8 g of compound (7-1).

NMR spectrum of compound (7-1):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.7 to3.5(1H), 3.3 to 3.1(1H), 2.8-2.6(1H), 1.3(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −55(3F),−83(50F), −88(52F), −90(2F), −110 to −117(2F), −125(52F).

Mean value of x: 13.

Ex. 2-4

Into a 200 mL three-necked flask, the system in which was replaced withnitrogen, 13.7 mL of a 0.7 mol/L ether solution of allyl magnesiumbromide and 45 mL of AK-225 were put, followed by stirring at 25° C. 9.5g of the compound (7-1) obtained in Ex. 2-3 diluted with 40 mL of AK-225was put into the three-necked flask little by little, followed bystirring overnight. The obtained crude product was quenched with a 1mol/L hydrochloric acid aqueous solution, followed by liquid separationwith AK-225, and the resulting organic layer was concentrated andpurified by silica gel column chromatography to obtain 9.0 g of compound(2-2).

NMR spectrum of compound (2-2):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 6.0 to5.8(3H), 5.3 to 4.6(6H), 2.8 to 2.2(4H), 2.0 to 1.7(4H), 1.4 to 1.3(1H),0.4 to 0.2(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −55(3F),−83(50F), −88(52F), −90(2F), −112 to −118(2F), −125(52F).

Mean value of x: 13.

Ex. 2-5

Into a 50 mL eggplant flask, 1 g of the compound (2-2) obtained in Ex.2-4, 0.10 g of trimethoxysilane, 0.0010 g of aniline, 1 g of AC-6000 and0.0033 g of a platinum/divinyltetramethyldisiloxane complex were put,followed by stirring at 25° C. overnight. The mixture was concentratedto obtain 1 g of compound (1-2).

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.7 to3.5(27H), 2.2 to 1.9(2H), 1.6 to 1.3(9H), 0.8 to 0.5(10H), 0.2 to 0(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −55(3F),−83(50F), −88(52F), −90(2F), −112 to −117(2F), −125(52F).

Mean value of x: 13.

Ex. 3

Compound (4-2) was obtained in accordance with the method disclosed inEx. 11-3 in WO2017/038830 using the compound (3-1) obtained in Ex. 1-1.

Mean value of x: 13, number average molecular weight of compound (4-2):5,400.

Ex. 4

Compound (1-3) was prepared in the same manner as in Ex. 2-3 except thattrichlorovinylsilane was used instead of dichloromethylvinylsilane.

Ex. 5-1

Into a 200 mL eggplant flask, 5.02 g of compound (6-0), 6.16 g oftriethylamine, 0.080 g of dimethylaminopyridine and 100 mL oftetrahydrofuran were put, followed by stirring in an ice bath. Then,10.9 g of di-tert-butyl dicarbonate was put, and the temperature of thereaction system was increased to 25° C., followed by stirring for onehour. Liquid separation was conducted with ethyl acetate and water, andthe resulting organic solvent layer was concentrated. The obtained crudeproduct was purified by silica gel column chromatography to obtain 7.90g (yield: 87%) of compound (6-2).

NMR spectrum of compound (6-2):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: tetramethylsilane (TMS)) δ(ppm): 6.1(1H), 5.9(1H), 4.5(1H), 3.2-2.5(5H), 2.2(1H), 1.8(1H),1.4(9H), 1.2(1H), 0.5(1H).

Ex. 5-2

Into a 1 L autoclave, 7.17 g of the compound (6-2) obtained in Ex. 5-1and 800 mL of toluene were put, followed by freeze deaeration, and 16 gof ethylene was put until the pressure gauge of the autoclave reached0.4 MPa [gauge]. A solution having 0.40 g ofbenzylidene{1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene}dichloro(tricyclohexylphosphine)ruthenium(Grubbs second-generation catalyst) dissolved in 5 mL of toluene wasinjected, followed by stirring at 25° C. for 22 hours. The mixture waspurified by silica gel column chromatography to obtain 1.1 g (yield:15%) of compound (6-3).

NMR spectrum of compound (6-3):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 5.8(2H),4.9(4H), 3.1(2H), 2.7(1H), 2.5(1H), 2.2(1H), 2.0(2H), 1.5-1.0(11H).

Ex. 5-3

Into a 200 mL eggplant flask, 1.1 g of the compound (6-3) obtained inEx. 5-2 and 50 mL of methylene chloride were put, followed by stirringin an ice bath. Then, 1.6 g of trifluoroacetic acid was put, followed bystirring at 25° C. for one hour. Then, 50 mL of a 10% sodium hydroxideaqueous solution was put, followed by stirring. Liquid separation wasconducted, and the resulting organic layer was dehydrated over magnesiumsulfate, and the magnesium sulfate was removed by filtration. Theorganic layer was concentrated to obtain 0.58 g (yield: 87%) of compound(6-4).

NMR spectrum of compound (6-4):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 5.8(2H),5.0(4H), 3.6(2H), 3.7(2H),3.5(2H), 2.2-1.9(3H), 1.4-1.0(2H).

Ex. 5-4

Into a 100 mL eggplant flask, 0.29 g of the compound (6-4) obtained inEx. 5-3, 5.0 g of compound (3-0) obtained by the method in Ex. 2-3 inWO2013/121984 and 5.1 g of AC-6000 were put, followed by stirring at 60°C. for 2 days. The obtained crude product was purified by silica gelcolumn chromatography to obtain 4.30 g (yield: 89%) of compound (2-11).

NMR spectrum of compound (2-11):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 5.7(2H),4.9(4H), 3.4(1H), 3.2(1H), 2.7(1H), 2.5(1H), 2.2(1H), 1.9(2H),1.4-1.0(2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −56(3F),−83(58F), −88(58F), −91(2F)-120(2F), −126(58F).

Ex. 5-5

Into a 50 mL eggplant flask, 1.1 g of the compound (2-11) obtained inEx. 5-4, 0.073 g of trimethoxysilane, 0.0001 g of aniline, 1.0 g ofAC-6000 and 0.0033 g of aplatinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were put,followed by stirring at 25° C. overnight. The solvent and the like weredistilled off under reduced pressure to obtain 1.1 g (yield: 100%) ofcompound (2-12).

NMR spectrum of compound (2-12):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.2(2H),2.3-1.4(5H), 1.2-0.5(10H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −56(3F),−83(58F), −88(58F), −91(2F)-120(2F), −126(58F).

Ex. 5-6

Into a 50 mL three-necked flask, the system in which was replaced withnitrogen, 5 ml of a 0.7 mol/L ether solution of allyl magnesium bromideand 5 mL of dichloropentafloropropane (manufactured by AGC Inc., AK-225)were put, followed by stirring at 0° C. 1.0 g of the compound (2-12)obtained in Ex. 5-5 diluted with 50 mL of AK-225 was put into thethree-necked flask little by little, followed by stirring overnight. Theobtained crude product was quenched with a 1 mol/L hydrochloric acidaqueous solution, followed by liquid separation with AK-225, and theresulting organic layer was concentrated and purified by silica gelcolumn chromatography to obtain 0.8 g of compound (2-13).

NMR spectrum of compound (2-13):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 6.0(6H),5.0(12H), 3.2(2H), 2.3-1.1(17H), 1.1-0.5(10H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −56(3F),−83(58F), −88(58F), −91(2F)-120(2F), −126(58F).

Ex. 5-7

Into a 50 mL eggplant flask, 0.8 g of compound (2-13) obtained in Ex.5-6, 0.20 g of trimethoxysilane, 0.0020 g of aniline, 0.8 g of AC-6000and 0.003 g of a platinum/divinyltetramethyldisiloxane complex were put,followed by stirring at 25° C. overnight. The mixture was concentratedto obtain 0.80 g of compound (1-4).

NMR spectrum of compound (1-4):

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm):3.8-3.2(56H), 2.1-0.5(51H)

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −56(3F),−83(58F), −88(58F), −91(2F)-120(2F), −126(58F).

Ex. 6

Compound (1-5) was prepared in the same manner as in Ex. 5-5 except thatdichloromethylvinylsilane was used instead of trichlorovinylsilane.

Ex. 7 to 12 Production and Evaluation of Article

Using the compound obtained in each of Ex. 1 to 6, a substrate wassurface-treated to obtain an article in each of Ex. 7 to 12. As thesurface treatment method, in each Ex., the following dry coating methodwas employed. As the substrate, chemically tempered glass was used. Withrespect to the obtained article, evaluations were carried out by thefollowing methods. The results are shown in Table 1.

(Dry Coating Method)

The dry coating was carried out by using a vacuum deposition apparatus(manufactured by ULVAC Co., VTR-350M) (vacuum deposition method). 0.5 gof the compound obtained in each of Ex. 1 to 6 was filled in a boat madeof molybdenum in the vacuum deposition apparatus, and inside of thevacuum deposition apparatus was evacuated to a level of at most 1×10⁻³Pa. The boat having the compound placed therein, was heated at atemperature raising rate of at most 10° C./min, and at the time when thevapor deposition rate by a quartz oscillator film thickness meterexceeded 1 nm/sec, the shutter was opened to initiate film deposition onthe surface of a substrate. When the film thickness became about 50 nm,the shutter was closed to terminate film deposition on the surface ofthe substrate. The substrate on which the compound was deposited, wassubjected to heat treatment at 200° C. for 30 minutes, followed bywashing with AK-225 to obtain an article having a surface layer on thesurface of the substrate.

(Wet Coating Method)

The compound obtained in each of Ex. 1 to 6, and C₄F₉OC₂H₅ (manufacturedby 3M, Novec (registered trademark) 7200) as a medium, were mixed toprepare a coating liquid having a solid content concentration of 0.05%.A substrate was dipped in the coating liquid and allowed to stand for 30minutes, whereupon the substrate was taken out (dip coating method). Thecoating film was dried at 200° C. for 30 minutes and washed with AK-225,to obtain an article having a surface layer on the surface of thesubstrate.

(Evaluation Methods)

<Method for Measuring Contact Angle>

The contact angle of about 2 μL of distilled water or n-hexadecaneplaced on the surface of the surface layer, was measured by using acontact angle measuring apparatus (manufactured by Kyowa InterfaceScience Co., Ltd., DM-500). Measurements were conducted at fivedifferent points on the surface of the surface layer, and the averagevalue was calculated. For the calculation of the contact angle, a 2θmethod was employed.

<Initial Contact Angle>

With respect to the surface layer, the initial water contact angle andthe initial n-hexadecane contact angle were measured by theabove-described measuring method. The evaluation standards are asfollows.

Initial Water Contact Angle:

⊚ (excellent): at least 115 degrees.

◯ (good): at least 110 degrees and less than 115 degrees.

Δ (acceptable): at least 100 degrees and less than 110 degrees.

× (poor): less than 100 degrees.

Initial n-Hexadecane Contact Angle:

⊚ (excellent): at least 66 degrees.

◯ (good): at least 65 degrees and less than 66 degrees.

Δ (acceptable): at least 63 degrees and less than 65 degrees.

-   -   × (poor): less than 63 degrees.        <Light Resistance>

To the surface layer, by means of a tabletop xenon arc lamp typeaccelerated light resistance testing machine (manufactured by Toyo SeikiSeisaku-sho, Ltd., SUNTEST XLS+), light (650 W/m², 300 to 700 nm) wasapplied at a black panel temperature of 63° C. for 1,000 hours,whereupon the water contact angle was measured. The smaller the decreasein water contact angle after the accelerated light resistance test, thesmaller the decrease in performance due to light, and the better thelight resistance. The evaluation standards are as follows.

⊚ (excellent): The change in water contact angle after the acceleratedlight resistance test is at most 2 degrees.

◯ (good): The change in water contact angle after the accelerated lightresistance test is more than 2 degrees and at most 5 degrees.

Δ (acceptable): The change in water contact angle after the acceleratedlight resistance test is more than 5 degrees and at most 10 degrees.

× (poor): The change in water contact angle after the accelerated lightresistance test is more than 10 degrees.

<Abrasion Resistance>

With respect to the surface layer, in accordance with JIS L0849: 2013(ISO 105-X12: 2001), using a reciprocating traverse testing machine(manufactured by KNT Co.), steel wool Bon Star (#0000) was reciprocated10,000 times under a pressure of 98.07 kPa at a speed of 320 cm/min,whereupon the water contact angle was measured. The smaller the decreasein water repellency (water contact angle) after the friction, thesmaller the decrease in performance due to friction, and the better theabrasion resistance. The evaluation standards are as follows.

⊚ (excellent): The change in water contact angle after reciprocation of10,000 times is at most 2 degrees.

◯ (good): The change in water contact angle after reciprocation of10,000 times is more than 2 degrees and at most 5 degrees.

Δ (acceptable): The change in water contact angle after reciprocation of10,000 times is more than 5 degrees and at most 10 degrees.

-   -   × (poor): The change in water contact angle after reciprocation        of 10,000 times is more than 10 degrees.        <Light Resistance+Abrasion Resistance>

After the above light resistance test, the above abrasion resistancetest was conducted, and evaluation was conducted based on evaluationstandards for abrasion resistance (steel wool).

<Chemical Resistance (Alkali Resistance)>

The article was immersed in a 1N aqueous sodium hydroxide solution (pH:14) for 5 hours, then washed with water and air-dried, whereupon thewater contact angle was measured. The smaller the decrease in watercontact angle after the test, the smaller the decrease in performancedue to alkali, and the better the alkali resistance. The evaluationstandards are as follows.

⊚ (excellent): The change in water contact angle after the alkaliresistance test is at most 2 degrees.

◯ (good): The change in water contact angle after the alkali resistancetest is more than 2 degrees and at most 5 degrees.

Δ (acceptable): The change in water contact angle after the alkaliresistance test is more than 5 degrees and at most 10 degrees.

× (poor): The change in water contact angle after the alkali resistancetest is more than 10 degrees.

<Chemical Resistance (Salt Water Resistance)>

The salt spray test was carried out in accordance with JIS H8502. Thatis, the article was exposed to salt atmosphere in a salt spray tester(manufactured by Suga Test Instruments Co., Ltd.) for 300 hours, andthen, the water contact angle was measured. The smaller the decrease inwater contact angle after the test, the smaller the decrease inperformance due to salt water, and the better the salt water resistance.The evaluation standards are as follows.

⊚ (excellent): The change in water contact angle after the salt spraytest is at most 2 degrees.

◯ (good): The change in water contact angle after the salt spray test ismore than 2 degrees and at most 5 degrees.

Δ (acceptable): The change in water contact angle after the salt spraytest is more than 5 degrees and at most 10 degrees.

× (poor): The change in water contact angle after the salt spray test ismore than 10 degrees.

<Fingerprint Stain Removability>

An artificial fingerprint liquid (liquid comprising oleic acid andsqualene) was deposited on a flat surface of a silicon rubber plug, andthen, extra oil was wiped off by a nonwoven fabric (manufactured byAsahi Kasei Corporation, BEMCOT (registered trademark) M-3), to preparea fingerprint stamp. The fingerprint stamp was placed on the surfacelayer and pressed under a load of 9.8 N for 10 seconds. The haze at aportion having a fingerprint put, was measured by a haze meter and takenas an initial value. With respect to the portion having a fingerprintput, using a reciprocating traverse testing machine (manufactured by KNTCo.) having tissue paper attached, wiping was carried out under a loadof 4.9 N. The value of haze was measured every one reciprocation forwiping, and the number of wiping times until the haze became at most 10%of the initial value, was measured. The smaller the number of wipingtimes, the easier the removal of fingerprint stain, and the better thefingerprint stain removability. The evaluation standards are as follows.

⊚ (excellent): The number of wiping times is at most 3 times.

◯ (good): The number of wiping times is from 4 to 5 times.

Δ (acceptable): The number of wiping times is from 6 to 8 times.

× (poor): The number of wiping times is at least 9 times.

TABLE 1 Ex. 7 8 9 10 11 12 Fluorinated ether compound (1-1) (1-2) (1-3)(1-4) (1-5) (4-2) Dry Initial contact Water ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ coating anglen-Hexadecane ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Light resistance ⊚ ⊚ ⊚ ⊚ ⊚ ∘ Abrasionresistance ∘ ⊚ ⊚ ∘ ∘ ∘ Light resistance + abrasion resistance Δ ∘ ∘ ∘ ∘× Wet Initial contact Water ⊚ ⊚ ⊚ ⊚ ⊚ ∘ coating angle n-Hexadecane ⊚ ⊚ ⊚⊚ ⊚ ⊚ Light resistance ⊚ ⊚ ⊚ ⊚ ⊚ ∘ Abrasion resistance ∘ ⊚ ⊚ ∘ ∘ ∘ Lightresistance + abrasion resistance Δ ∘ ∘ ∘ ∘ × Chemical Alkali resistance∘ ∘ ∘ ∘ ∘ ∘ resistance Salt water resistance ∘ ⊚ ⊚ ∘ ∘ ∘ Fingerprintstain removability ⊚ ⊚ ⊚ ⊚ ⊚ ⊚

It was confirmed that in Ex. 7 to 11 in which the compound (1) was used,initial water/oil repellency, abrasion resistance, fingerprint stainremovability, light resistance and chemical resistance were excellent.Particularly, abrasion resistance after the light resistance test wasexcellent, and it was confirmed that light resistance was more excellentthan in Ex. 6 in which a conventional fluorinated ether compound wasused.

INDUSTRIAL APPLICABILITY

The fluorinated ether compound of the present invention is useful forvarious applications for which it is required to impart lubricity andwater/oil repellency. For example, it may be used for a display inputdevice such as a touch panel, surface protective coating on atransparent glass or transparent plastic member, kitchen antifoulingcoating, water repellent moistureproof coating or antifouling coating onelectronic device, a heat exchanger or a battery, toiletry antifoulingcoating, coating on a member which requires liquid repellency whileconducting electricity, water repellent/waterproof/water sliding coatingon a heat exchanger, or a surface low friction coating on the inside ofa vibrating strainer or a cylinder, etc. More specific examples ofapplication include a front protective plate, an antireflection plate, apolarizing plate, an antiglare plate or a surface thereof having anantireflection film, of a display, an apparatus having a display inputdevice of which the screen is operated by human fingers or hands, suchas a touch panel sheet or a touch panel display of an apparatus such asa mobile phone or a personal digital assistant, a decorative buildingmaterial for restroom, bathroom, lavatory, kitchen and the like,waterproof coating for a wiring board, water repellent/waterproofcoating on a heat exchanger, water repellent coating on a solar cell,waterproof/water repellent coating on a printed wiring board,waterproof/water repellent coating for an electronic equipment casing oran electronic member, insulating property-improving coating on a powertransmission line, waterproof/water repellent coating on a filter,waterproof coating on an electromagnetic wave absorption material or anacoustic material, antifouling coating for bathroom, kitchen instrumentand toiletry, water repellent/waterproof/water sliding coating on a heatexchanger, surface low-friction coating on the inside of a vibratingstrainer or a cylinder, surface protective coating on a machinecomponent, a vacuum apparatus component, a bearing component, anautomobile component, an industrial tool, etc.

This application is a continuation of PCT Application No.PCT/JP2018/047628, filed on Dec. 25, 2018, which is based upon andclaims the benefit of priority from Japanese Patent Application No.2017-251611 filed on Dec. 27, 2017. The contents of those applicationsare incorporated herein by reference in their entireties.

What is claimed is:
 1. A fluorinated ether compound, which is a compoundrepresented by the following formula (1):A¹—R—(R^(f1)O)_(m)—A²  (1) wherein A¹ is a C₁₋₂₀ perfluoroalkyl group,A² is a group represented by the following formula (g1-1), a grouprepresented by the following formula (g1-2) or a group represented bythe following formula (g1-3), R^(f1) is a fluoroalkylene group, m is aninteger of from 2 to 500, and (R^(f1) O)_(m) may consist of two or moretypes of R^(f1)O differing in the number of carbon atoms:—Q¹[—C(R¹¹)_(b) (R¹²)_(3-b)]_(a)   (g1-1)—Q¹[—N(R¹¹)₂ ]_(a)   (g1-2)—Q¹[—Z(R¹¹)_(n)]_(a)   (g1-3) wherein Q¹ is a fluorohydrocarhon grouphaving a CF₂ or CHF group which bonds with a terminal O of the group—O—(R^(f1)O)_(m) of formula (1), and optionally comprising a bond Bwherein the bond B is —C(O)NR—, wherein R is a hydrogen atom, a C₁₋₆alkyl group or a phenyl group, Z is a group haying a n+1 valent cyclicstructure haying a carbon atom or a nitrogen atom to which Q¹ isdirectly bonded and a carbon atom or a nitrogen atom to which R¹¹ isdirectly bonded, R¹¹ is a group represented by the following formula(g2), R¹² is a hydrogen atom, a halogen atom, a hydroxy group or amonovalent organic group, a is an integer of from 1 to 3, b is 2 or 3, nis an integer of at least 2, when a is at least 2, the a [—C(R¹¹)_(b)(R¹²)_(3-b) ] may be the same or different, the a [—N(R¹¹ )₂] may be thesame or different, and the a [—Z(R¹¹)_(n)] may be the same or different,and a plurality of R¹¹ may be the same or different;—Q²—Si(R²¹)_(c)(R²²)_(d)(R²³)_(e)   (g2) wherein Q² is a single bond oran alkylene group, R²¹ is a group represented by the following formula(g3), R²² is an alkyl group, R²³ is a hydrolyzable group or a hydroxygroup, c, d and e are each independently an integer of from 0 to 3,c+d+e is 3, in at least one R¹¹ among a plurality of R¹¹ in A², c is 2or 3, when c is at least 2, the c R²¹ may be the same or different, whend is at least 2, the d R²² may be the same or different, when e is atleast 2, the e R²³ may be the same or different;—Q³—Si(R³¹)_(3-g)(R³²)_(g)   (g3) wherein Q³ is an alkylene group, R³¹is an alkyl group, R³² is a hydrolyzable group or a hydroxy group, g isan integer of from 1 to 3, when g is 1, the two R³¹ may be the same ordifferent, and when g is at least 2, the g ³² may be the same ordifferent.
 2. The fluorinated ether compound according to claim 1,wherein a is
 1. 3. The fluorinated ether compound according to claim 1,wherein Q² is a single bond or a C₁₋₆ alkylene group.
 4. The fluorinatedether compound according to claim 1, wherein Q³ is a C₂₋₆ alkylenegroup.
 5. A fluorinated ether composition comprising at least one typeof the fluorinated ether compound as defined in claim 1, and otherfluorinated ether compound.
 6. A coating liquid comprising thefluorinated ether compound as defined in claim 1, and a liquid medium.7. An article comprising a substrate and a surface layer formed of thefluorinated ether compound as defined in claim 1 on a surface of thesubstrate.
 8. The article according to claim 7, which has the surfacelayer on a surface of a member constituting a plane of a touch panel tobe touched with fingers.
 9. A method for producing an article, whichcomprises treating a surface of a substrate by dry coating method usingthe fluorinated ether compound as defined in claim 1 to form a surfacelayer formed of the fluorinated ether compound on the surface of thesubstrate.
 10. A method for producing an article, which comprisesapplying the coating liquid as defined in claim 6 to a surface of asubstrate by wet coating method, followed by drying to form a surfacelayer formed of the fluorinated ether compound on the surface of thesubstrate.
 11. A fluorinated ether compound, which is a compoundrepresented by the following formula (2):A¹⁰—O—(R^(f1)O)_(m)—A²⁰   (2) wherein A¹⁰ is a C₁₋₂₀ perfluoroalkylgroup, A²⁰ is a group represented by the following formula (g4-1), agroup represented by the following formula (g4-2) or a group representedby the following formula (g4-3), R^(f1) is a fluoroalkylene group, m isan integer of from 2 to 500, and (R^(f1)O)_(m) may consist of two ormore types of R^(f1)O differing in the number of carbon atoms:—Q¹[—C(R¹¹⁰)_(b)(R¹²)_(3-b)]_(a)   (g4-1)—Q¹[—N(R¹¹⁰)₂]_(a)   (g4-2)—Q¹[—Z(R¹¹⁰)_(n)]_(a)   (g4-3) wherein Q¹ is a fluorohydrocarbon grouphaving a CF₂ or CHF group which bonds with a terminal O of the group—O—(R^(f1)O)_(m) of formula (1), and optionally comprising a bond Bwherein the bond B is —C(O)NR—, wherein R is a hydrogen atom, a C₁₋₆alkyl group or a phenyl group, Z is a group having a n+1 valent cyclicstructure having a carbon atom or a nitrogen atom to which Q¹ isdirectly bonded and a carbon atom or a nitrogen atom to which R¹¹⁰ isdirectly bonded, R¹¹⁰ is a group represented by the following formula(g5), R¹² is a hydrogen atom, a halogen atom, a hydroxy group or amonovalent organic group, a is an integer of from 1 to 3, b is 2 or 3, nis an integer of at least 2, when a is at least 2, the a[—C(R¹¹⁰)_(b)(R¹²)_(3-b)] may be the same or different, the a[—N(R¹¹⁰)₂] may he the same or different, and the a [—Z(R¹¹⁰)_(n)] maybe the same or different, and a plurality of R¹¹⁰ may be the same ordifferent;—Q²—Si(R²¹⁰)_(c)(R²²)_(d)(R²³)_(e)   (g5) wherein Q² is a single bond oran alkylene group, R²¹⁰ is a group represented by the following formula(g6), R²² is an alkyl group, R²³ is a hydrolyzable group or a hydroxygroup, c, d and e are each independently an integer of from 0 to 3,c+d+e is 3, in at least one R¹¹⁰ among a plurality of R¹¹⁰ in each ofA¹⁰ and A²⁰, c is 2 or
 3. when c is at least 2, the c R²¹⁰ may be thesame or different, when d is at least 2, the d R²² may be the same ordifferent, when e is at least 2, the e R²³ may be the same or different;—Q³⁰—CH═CH₂   (g6) wherein Q³⁰ is a single bond or an alkylene group.